DE2659422B2 - Liquid dye compositions, their preparation and use - Google Patents

Description

R ₁ -C-

R ₁ COONH ₄

(D

-C-

-c-

R ₂ COONH ₄

C - C

(in

R ,,

contains, where Ri is a hydrogen atom, a lower alkyl group or the group -COONH ₄ , R _{2 is} a hydrogen atom or a lower alkyl group and R3 is a hydrogen atom, a lower alkyl group or the group - CH ₂ - COONH ₄ .

4. Composition according to claim t, characterized in that the water-soluble polymer a copolymer of 3 to 50 mol% of at least one repeating structural unit of the formula

wherein Ri is a hydrogen atom, a lower alkyl group or the group -COONH ₄ , R _{2 is} a hydrogen atom or a lower alkyl group and Rj is a hydrogen atom, a lower alkyl group or the group -CH ₂ - COONH ₄ , and 97 to 50 mol% of at least one repeating structural unit derived from a monomer having an ethylenically unsaturated bond represented by the formula

wherein R ₄ and R ^ independently of one another denote a hydrogen atom or a lower-alkyl group and Re is a lower-alkoxy group, a lower-acyloxy group or a lower-alkoxycarbonyl group.

5. Composition according to claim 1, characterized in that the water-soluble polymer has a number average molecular weight of 2500 to 5000.

6. Composition according to claim I, characterized in that the water-miscible organic solvent from the group of alcohols, Ethers and esters is chosen

7. Composition according to claim 1, characterized in that the water-miscible solvent is a monohydric or polyhydric alcohol with a molecular weight not exceeding 600

8. The composition according to claim 1, characterized in that the water-insoluble or Dyes with limited solubility are selected from the group of disperse dyes, vat dyes, metallized dyes or metal complex dyes and cationic dyes.

9. Composition according to claim 1, characterized in that the amount of in water soluble polymers 80 to 200 Gev. Parts, the amount of water-miscible organic Solvent 80 to 1000 parts by weight and the amount of water at most 250 parts by weight, respectively based on i 00 parts by weight of the dye.

10. A process for the preparation of a liquid dye composition with a uniformly and finely dispersed, water-insoluble or sparingly soluble dye, characterized in that one is a water-soluble polymer with - COONH ₄ groups, a water-miscible organic solvent and optionally water and a water-insoluble or sparingly soluble dye is mixed and the mixture is ground.

11. Use of the compositions according to one of claims 1 to 9 for printing pastes or dye baths for printing or dyeing textile material.

The invention relates to new dye compositions of the liquid type which are insoluble or water-insoluble contain poorly water-soluble dyes which are free of dispersants and have improved coloring properties, a process for their production, and the use of these compositions for printing pastes or dye baths for printing or Dyeing of textile material.

Dyes that are insoluble in water or have limited solubility in water, such as disperse dyes or Vat dyes are generally dispersed in water with dispersants when used for coloring or used for printing on textile objects. This practice has the disadvantage that the dispersants, which are necessary to disperse the dyes in water, the Adversely affect the dyeing properties of these dyes for textile objects. For example synthetic fibers such as polyester fibers, dyed or printed, the color yield is not entirely satisfactory and it cannot be satisfactorily high Fixation of the dye on the fiber or fabric can be obtained. In addition, those tend to obtained colorations to take on a cloudy tone. For this reason one has so far predominantly Dyes used in very high concentrations or together with fixation accelerators. When using water-insoluble or water-insoluble dyes together with

The im general hygroscopic nature of surfactants used as dispersants, that the printed and dried printing paste absorbs water and causes bleeding. This also leads to to contamination when folding or winding.

The object of the invention is to provide a liquid dye composition which does not contain a dispersant which has the ability to be dyed with an in Water-insoluble or limited water-soluble dye adversely affected and improved Leads coloring properties and, in particular, leads to coloring with a high color yield, superior fixation of the dye, good color fastness and bright colors

The dye composition has superior thermal stability and storage properties, being insoluble in water or dye with limited solubility is dispersed very finely and evenly in a liquid medium.

The invention also relates to the manufacture of the composition.

The invention also relates to the use of the composition for printing pastes or dye baths for printing or dyeing textile materials.

According to the invention, a liquid dye composition is created which consists of a water-insoluble or sparingly soluble dye, dispersed in a carrier, which consists of a water-soluble polymer with - COONH ₄ groups and a water-miscible organic solvent and optionally water

The first feature of the invention is that a water-soluble polymer having - GGONH ₄ groups is used in place of an ordinary dispersant for preparing a dye composition by dispersing a water-insoluble or sparingly soluble dye in water.

It has been found that the use of a water-soluble polymer in accordance with the invention considerably improves the dispersion and the color yield of a dye in textile materials, although this has not yet been clearly explained. The water-soluble polymer used according to the invention can be selected from a wide range of - COOHN ₄ -containing polymers which have a solubility in water of at least 100 g / 100 g of water, preferably of at least 200 g / 100 g of water, and - COONH ₄ - Have groups as pendent side chains. The number of - COONH ₄ groups is not critical as long as these groups make the polymer soluble in water. In general, the polymer can contain at least 2, preferably 3 to 20, particularly preferably 4 to 15 - COONH4 groups per 100 g of the polymer.

Typical such —COONH4 -containing, water-soluble polymers contain at least 3 mole percent of at least one repeating structural unit the formula

-C-

R ₂ COONH ₄

(D

or the group -COONH ₄ is, R2 is a hydrogen atom, a lower alkyl group and R _{3 is} a hydrogen atom, a lower alkyl group or the group -CH ₂ -COONK ₄

In the present specification and claims, the term "low" means that the Number of carbon atoms in the so-called group or compound up to 7, preferably up to 5 amounts to

In the above formula (I), the lower alkyl group may be straight or branched chain and includes for example methyl, ethyl, n- or isopropyl and n-, iso-, sec- or tert-butyl. It is particularly preferred Msthyl. Specific examples of the recurring

Unit of formula (I) are:

CH ₂ -CH-

COONH _{1 y}

CH ₃

-CH-CH-

COONH ₄ ;

-CH ₂ -C

COONH _{4 /} CH ₂ -COONH _{4 -CH 2} -C

COONH ₄ - / - CH CH-

\ COONH ₄ COONH ₄

CH ₃
-fC

CH

_and d

COONH ₄ COONH ₄ ,

CH ₃ CH ₃ -KH C

COONH _{4 y}

Thus, preferred groups of the repeating unit represented by the formula (I) are represented by the following formula

In Rm

-CH

COONH ₄

(la)

wherein Ri is a hydrogen atom, a lower alkyl group represented, wherein Rn denotes a hydrogen atom, a methyl group or a -COONH4 group, and R31 a hydrogen atom, a methyl group or a

- CH2 — COONPV group represents, and in particular by the following formula

+ CH-

-c-

COONH ₄ ,

(Ib)

wherein R12 and R32 independently of one another are a hydrogen atom or represent a methyl group.

The polymer nvt the repeating structural unit of the form; l (I) can be a homopolymer of only one type of repeating unit, however, it is advantageously used generally in the form of a copolymer with at least one repeating unit of the formula (I). The copolymer can have two or more structural units Formula (I) or both at least one repeating unit of the formula (I) and at least one other have a recurring unit. The latter is particularly useful and in this case it can Copolymers at least 3 mole percent, usually at most 50 mole percent, preferably 5 to J5 Mol percent, particularly preferably 7 to 15 mol percent, contain the repeating structural unit of the formula (I).

The other repeating structural unit present in the - COONHr-containing copolymers j » can be, is expediently a unit that is different from a monomer with an ethylenically unsaturated Bond. Typical examples of the monomer having an ethylenically unsaturated bond include Monomers of Formula 3>

Ri R ₅

wherein R * and R5 independently of one another are a hydrogen atom or a lower alkyl group and R6 is a lower alkoxy group, a lower acyloxy group or represents lower alkoxycarbonyl group. .r>

In formula (II) the “lower alkyl group” can be straight or branched chain and includes, for example, methyl, ethyl, n- or iso-propyl and n-, iso-, sec- or tert-butyl groups. Methyl is particularly preferred. The "lower alkoxy group" includes, for example, methoxy, ethoxy, n- or iso-propoxy and n-, iso-, sec- or tert-butoxy. The "lower acyloxy group" is a group of the Forme! -OCOR7, where R _{7 is} a lower alkyl group, such as acetyloxy or propionyloxy. The "lower alkoxycarbonyl group" is a group of the formula -COORg, in which Rg is a lower alkyl group, such as methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl and n-, iso-, sec- or tert-butoxycarbonyl.

So preferred groups of the monomer of <, o Formula (II) by the following formula

R ₄ ,

Il

(Mn)

represents a hydrogen atom or a methyl group, and Rei represents a lower alkoxy group, an acetyloxy group or represents a lower alkoxycarbonyl group.

Typical examples of monomers of the formula (N) or (Ha) are methyl acrylate, ethyl acrylate, n-, iso-, sec- or tert-butyl acrylate, n- or iso-propyl acrylate, Vinyl acetate, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, Methyl crotonate, ethyl crotonate, ethyl isocrotonate, ethyl itaconate, methyl methacrylate, ethyl methacrylate, n-, iso-, sec- or terL-butyl methacrylate and n- or iso-propyl methacrylate. Among these are vinyl acetate and lower alkyl esters of acrylic acid are particularly preferred.

The molecular weight of the water-soluble polymer used in the present invention is not critical. However, it is generally difficult to incorporate very high molecular weight polymers into To obtain water soluble form and therefore it is generally preferred that the water soluble poly mers that use according to the invention! be, a number average molecular weight not more than 10,000. On the other hand, the lower limit of the Molecular weight is not critical and the polymer, although it depends on the type of polymer, has preferably a number average molecular weight of at least 2000, preferably 2500 to 5000 and particularly preferably 2800 to 3600.

The water-soluble polymers with -COONH ₄ groups can easily be produced. For example, they can easily be prepared by polymerizing at least one carboxyl-containing monomer of the formula

H") r:

C = C

(III)

COOH

in which R41 and Rs ₁ independently of one another in which R'i denotes a hydrogen atom, a lower alkyl group or a carboxyl group, R ' ₃ denotes a hydrogen atom, a lower alkyl group or the group -CH ₂ -COOH, and R _{2 is} as defined above with optionally at least one monomer of the formula (II) or (Ua) and neutralizing the resulting carboxyl group-containing polymers with ammonia or an aqueous solution of ammonia.

Typical examples of carboxyl group-containing monomers of the formula (HI) include crotonic acid, Acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid and tiglic acid. You can either can be used alone or in combination of two or more. Among these are the crotonic acid, Acrylic acid, methacrylic acid and itaconic acid are preferred, and crotonic acid is particularly suitable.

The polymerization can be carried out by any known procedure, such as the polymerization in solution, the Polymerization carried out in emulsion, polymerization in suspension or polymerization in bulk In general, the method of polymerization is in solution to achieve molecular weights of the above range is well suited.

Particularly useful monomer combinations for the preparation of the polymers are combinations of the Carboxyl group-containing monomers of the formula (III), in particular crotonic acid, with at least one Monomers selected from the group of Vinylace-

did, lower alkyl esters of acrylic acid and lower alkyl esters of methacrylic acid.

Another characteristic feature of the present invention is that a with water miscible organic solvent or a mixture of water and one miscible with water organic solvent as a liquid medium for dispersing the insoluble or limited in water Soluble dyes are used, which makes them insoluble or sparingly soluble in water Dyes are evenly dispersed in a very finely divided form in the liquid dye preparation can.

The water-miscible organic solvent can be any organic solvent which is inert to the dyes and does not substantially dissolve the dyes, even if it dissolves the dyes, the solubility of the dyes is less than 3% by weight . ίϊί'ι äiigciViciücii lsi it is favorable to choose uas ei iiiiuuilgsge according to organic solvents used from alcohols, ethers and esters. Examples of alcohols that can be used are monohydric lower alcohols such as methanol, ethanol, n- or iso-propanol, n- or tert-alcohol or n- or tert-butyl alcohol or allyl alcohol; polyhydric alcohols such as ethylene glycol. 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, α-methyl-2,4-pentanediol. 2,4-pentanediol. 2,5-hexanediol, 2,4-heptanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol (molecular weights 200, 300, 400 or 600) or glycerine; and ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monobutyl ether. Examples of the ethers are diethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether and dioxane. Examples of the esters are ethyl acetate and amyl acetate. These solvents can be used either alone or in combination of two or more.

Particularly preferred organic solvents which can be used according to the invention are Alcohols with a boiling point of at least 60 ° C, preferably monohydric or polyhydric alcohols with a molecular weight not exceeding 600. Ethylene glycol has proven to be a very useful one Medium proved to keep the liquid dye composition stable for long periods of time.

The water-miscible organic solvent can be used as such or as a dispersing medium in the form a mixture with water.

The water-insoluble or sparingly soluble dyes which are used for the preparation of the Liquid dye compositions used are dyes that are not substantially in water dissolve and, for example, disperse dyes, vat dyes, metallized dyes or metal complex dyes and cationic dyes. Typical examples of these dyes are shown below.

Disperse dyes

CI. Disperse Yellow 71
CI Disperse Orange 73
C I. Disperse Red 83
C.! .Disperse Violet 56
CI. Disperse Blue 113
CI-Disperse Blue 198

Vat dyes

C. C. C. C. C.

Cationic dyes

C. r

C.
C.
C.

C.
C.
C.
C.
C.
C.

Vat Yellow 12 = C. 1.67 300
Vat Orange II = C. 1.70 405
Vat Red 41 = C. 1.73 300

Father Violet 15

.Vat Blue67

. Vat Blue 22 = C. 1.59 820

. Basic Yellow 24

.Basic Red 51

. Basic orange 33

. Basic Violet 34

.Basic Blue 7 = C. 1.42 595

Metallized dyes

.Acid Yellow 129
. Acid Orange 86
.Acid Red 211
.Acid Violet 73
.Acid Blue 171
.Acid Blue 188

The proportions of the ingredients in the liquid

.'-> Dye composition according to the invention can vary over a wide range depending on, for example, the intended use of the composition. In general, the proportion of the water-soluble Polymers at least 50 parts by weight per 100

jn part by weight of the dye, although depending on the species it of the polymer varies. While there is no specific upper limit ordering, using too much results Polymers fail to make corresponding improvements. Hence, the appropriate amount of the water-soluble one lies

3t polymers up to 250 parts by weight preferably at 80 to 200 parts by weight, particularly preferably at 100 to 150 parts by weight per 100 parts by weight of the Dye.

The amount of water miscible organic

4n solvent is not critical and may vary depending on for example, the type of solvent or the type of polymer and dye vary. in the generally the amount of the solvent is at least 50 parts by weight per 100 parts by weight of the

! i dye. The upper limit is preferably 1500 parts by weight. The appropriate amount of the organic solvent is usually from 80 to 1000 parts by weight per 100 parts by weight of the dye. If it is used in combination with water,

in this way its amount is preferably 80 to 200 parts by weight, preferably 100 to 150 parts by weight. In the absence of water, the amount of the organic solvent is advantageously 100 to 1000 Parts by weight, especially with 200 to 800 parts by weight

> 5 len.

If water is used, the amount of water is at most 250 parts by weight, preferably at most 200 parts by weight per 100 parts by weight of the dye.

The liquid composition according to the invention can be used directly for the purposes described below be used.

If desired, additives usually used for the production of printing pastes or dye baths can be added made of water-insoluble or sparingly soluble dyes are used, for example conditioning agents or improvers such as polyethylene wax in the liquid dye composition in

small amounts are incorporated (for example not more than 5 percent by weight, based on the Total weight of the dye composition).

The liquid dye composition of the present invention can by mixing the -COONH ^ containing polymer, the water-miscible organic solvent or both of the organic Solvent as well as water and the water-insoluble or partially soluble in water Dye and grinding the mixture are made. The marriage can usually take place in different ways known devices take place, such as a roller mill, ball mill, a .Sandmahlvorrichtung or a grinding device (attriter). The above ingredients are used in the specified proportions introduced into such a device in an optional order and in a sufficient manner to marry.

By the present invention, a dye composition in which the water-insoluble or sparingly soluble dye evenly distributed in very fine form, generally in the form of ultrafine particles with a size of less than 1 micron is present in a carrier (vehicle) made up of the -COOHN ^ -containing polymers and the water-miscible organic solvent with or without water.

The liquid dye composition of the present invention can be used in the form as it is obtained for Dyeing of textile materials can be used, it is advantageous to use a thickener or Water mixed and used in the form of a printing paste or a dye bath.

The printing paste can be mixed by mixing the liquid Dye composition can be prepared with a thickener. Thickeners, general used for the production of printing pastes are, for example, starch, sodium alginate, Gum arabic, tragacanth gum, etherified starch, carboxymethyl cellulose, polyvinyl alcohol and the in GB-PS 13 35 586 and in JP patent publication Synthetic resin pastes described in 18 914/72. In addition, synthetic resin pastes, that by complete neutralization of copolymers of maleic acid with at least one copolymerizable Monomers, such as vinyl acetate, lower alkyl vinyl ethers, lower alkyl acrylates or lower alkyl methacrylates, with ammonia or aqueous ammonia, and preferably an aqueous synthetic one Resin paste obtained by completely neutralizing a copolymer of 1 mol of maleic acid and 10 mol Vinyl acetate (with an average molecular weight of 2500 to 4000) with ammonia, was obtained, be used.

If necessary, it is possible to incorporate additives into the thickener. Examples of such additives are hydrotropic materials such as urea, glycerine, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or diethylene glycol monobutyl ether; Dye-dissolving agents such as thiodiethylene glycol; Color deepening auxiliaries, such as polyoxyethylene pentaerythritol or polyoxyethylene oleyl ether; and defoaming agents, such as octyl alcohol or decyl alcohol. Such Additives are used in the usual amounts.

In addition, the above-described water-soluble polymer may optionally be included in the thickener in an amount up to 10 percent by weight based on the weight of the basic diluent, can be incorporated to improve the feel of the dyed textile materials.

The thickening can be produced as an emulsion

and in such a case a "white spirit"

> (Turpentine oil substitute, light gasoline) (boiling point 170 to 180 ° C) and an emulsifier of the above paste are fed.

The mixing ratio between the liquid dye composition and the thickener

in can be varied over a wide range, depending on for example the printing method, the structure of the textile materials and the desired color consistency. The dye composition according to the invention can advantageously be included in any desired proportion

ii to be mixed with the thickener. However, will generally the dye composition in an amount of up to 50 parts by weight per hundred Parts by weight of the thickener mixed.

Textile materials can with the so produced

j »Printing paste according to any desired procedure can be printed. Printing can be performed using any flat screen printing machine, a rotary screen printing machine and a roller printing machine and the printed textile materials

2) can be done using any fixation method such as Steam fixation, dry heat fixation, or high temperature steam fixation can be treated and can be aftertreated in the usual way, for example by alkali soap treatment.

ίο The dye bath can also be mixed by mixing the liquid dye composition according to the invention can be prepared with water. The mixed portion can be varied over a wide range, depending on, for example, the structure of the textile material and

r, the desired color consistency. For example, the dye composition can be used in an amount of up to at 10 parts by weight per 100 parts by weight of water. If necessary, aids, for example leveling agents such as ammonium sulfate, anhydrous sodium sulfate or acetic acid or surface-active Means to be added in suitable amounts.

Textile objects or materials can be mixed with the dye bath by any desired method like dyeing on supports, high temperature dyeing or dyeing in a liquid stream.

The colored products are aftertreated in the usual way.

Textile materials with the inventive

-, o liquid dye composition printed or May be colored include, for example, natural Fibers such as cellulose fibers or wool; semi-synthetic fibers such as acetate diacetate or triacetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile or polypropylene fibers; and mixtures of these Fibers that are in the form of yarns, woven fabrics, knitted fabrics, or non-woven materials, or Fleece, etc. are present.

The liquid dye created according to the invention

bo composition contains the water-insoluble or sparingly soluble dye in the form of very finely and evenly dispersed particles and has superior thermal stability and storage stability on. It gives a good color yield and a superior dyeability regardless of the dyeing or printing method used and can result in dyed products with bright colors with great color fastness.

In addition, since the liquid dye composition of the present invention does not contain a dispersant, it has the advantage that no unpleasant side effects occur, as is the case with conventional ones Printing techniques are the case, such as bleeding, soiling when rubbing or surface defects or staining.

Another Vci part of the invention is that the liquid dye composition according to the invention has superior dyeing properties, the aftertreatment liquor has a small amount of unused dye and is easy to handle can.

In the following examples, the relative surface color density, the rub fastness and the Perspiration fastness determined by the following methods.

(1) Relative surface color density

The spectral reflectance ratio of the surface of a sample dye was determined using a Spectrophotometer (model 307 from Hitachi Limited) measured with a band width of 5 nm. The relative The surface density K / S was calculated according to the Kubelka-Munk equation [cf. P. K u b e I k a, F. M u η k, Z. Techn. Phus 12,593,1931]:

K / S =

2 rows

where R is the measured spectral reflectance ratio, that is, the reflectance ratio of a monochrome

Light. . ". ,,,,". ,, ..

(2) Investigation of the rubbing fastness

A test staining was carried out 100 times with a white test cloth under the following conditions under a Load of 200 g using an abrasion measuring device (crock meter II type from Nippon Senshoku Kigaki K. K.) rubbed the extent of the staining on the white examination tissue was rated using a gray scale with a graduation from 1 to 5.

Dry abrasion: The test was carried out with a dry white test cloth (cotton, Plain weave).

Wet abrasion: The test was carried out with a wet cloth (cotton, plain weave) carried out.

(3) Fastness to perspiration

Two stain samples were immersed in an artificial acidic or alkaline welding solution for 30 minutes

Table 1

immersed, and then inserted between two white cloths made of cotton-polyester-linen fabric. ^{The assembly was pressurized to 4.54 kg / cm 2} at 37 ± 5 ° C for 24 hours using a sweat tester, and the staining on the white cloth was rated performed from 1 to 5.

ίο Artificial acidic perspiration solution

L-histidine hydrochloride 0.5 g

Sodium chloride 5 g

Monosodium phosphate 2.2 g

To a mixture of the above compounds were added 15 ml of a Vio η-aqueous solution of sodium hydroxide to adjust the pH of the mixture to 5.5 together, and then lit, distilled water was added to a total volume of I liter.

Artificial alkaline sweat solution

L-hystidine hydrochloride 0.5 g

2) sodium chloride 5 g

Disodium phosphate 5 g

To a mixture of the above compounds, 25 ml of a '/ io η-aqueous solution of

κι sodium hydroxide added to the pH of the mixture to be adjusted to 8.0, after which distilled water was added to a total volume of 1 liter.

The -COON ^ -containing water-soluble polymers used in the following examples

jj were made as follows:

A reactor equipped with a stirrer, a reflux condenser and a nitrogen gas inlet was charged with the monomers of Table 1 in the amounts indicated, and 150 parts by weight of dioxane as a solvent and 0.02 part by weight of azobisisobutyronitrile as a polymerization initiator were added. The reaction mixture was polymerized under reflux (95 to 100 ⁰ C), until essentially no increase in the viscosity of the mixture occurred more

4-) (usually 6 to 8 hours). After the polymerization the dioxane was distilled off under reduced pressure. A sufficient amount of 28% aqueous Ammonia was added to the resulting polymer to completely neutralize it. The properties

) 0 of the resulting water-soluble polymers also listed in Table 1.

Polymers B. C. D. E. F. G H A. Monomers 5 10 Acrylic acid (parts by weight) 10 30th Itaconic acid (parts by weight) 10 10 10 8th Crotonic acid (parts by weight) 10 Methacrylic acid (parts by weight) 5 Ethyiacryate (part by weight) 40 5 5 IC 10 10 n-butyl acrylate (parts by weight) 50 85 65 80 80 80 80 92 Vinyl acetate (parts by weight)

13 14

continuation

Polymers

A B C D E F Γ, Η

Number of -COONHr groups 6.0 5.2 13.3 5.3 5.2 6.2 5.2 4.2 per 100 g of the polymer

Number average molecular weight 3400 2900 3000 2900 3000 3500 3300 2950

Percentage of a -COONH ^ contained 6.47 9.76 43.24 9.7 9.5 8.1 9.5 7.6 Monomer unit (mol%)

. I ₁ steel with a diameter of about 0.475 cm)

P ' ^e Γ. filled, mixed and dispersed for two hours.

The dyes, water-soluble polymers, with The evaluation of the obtained liquid dye pre-water Miscible organic solvents and parate by means of a grinder showed that the Water of Table 2 became a particle size of less than 1 in the dye particles in Table 2 specified amounts in a friction mill (Modeii microns and were very even. Even MA-15S from Mitsui Miike Seisakusho K. K., Umdre- jo when stored for more than 3 months at room temperature A heating speed of 120 rpm, the stainless steel balls hardly changed their dispersibility.

Table 2

[• Dye composition (parts by weight)

A B C D F. F G Il

C. C. C. C. C. C. C. C.

. Disperse Yellow 79 15

. Disperse Orange 73 15

. Disperse Blue 113 15

. Disperse Blue 198 15

. Disperse Yellow 42 15

. Vat Red 41 = C.I. 73 300 10

. Acid Violet 103 10

15th 10 10 45 45 40 20th 15th 10 15th 15th 20th 20th 15th 15th 10 5 5 5 5 5 5 10 5 5

Basic Orange 33 10

Polymer A 20

Polymer B 20

Polymeric C 20

Polymer D 20

Polymeric E 15

Polymeric F 15

Polymeric G 15

Polymeric H ethyl alcohol Isopropyl alcohol Ethylene glycol

Ethylene Glycol Monobutyl Ether 55555555

Water 30 30 30 30 10 30

. · Ι ₇ ^ur 'd 29 parts by weight of water were in a high

Example 2 introduced speed homogenizer and 15 minutes

A printing paste was applied in the following manner under 60 times at a speed of 5090 rpm

Application of the dye formed in Example 1 stirred formation of a printing paste A, which has a viscosity,

Composition A produced 12 parts by weight of etherified measured by means of a B-type viscometer

Starch, 0.5 part by weight of sodium metanitrosulfonate and 25 ° C of 850OcP.

87.5 parts by weight of water were uniformly mixed with a For comparison purposes, printing pastes I and II

Homogenizer at high speed below 65 in the same way as described above.

Formation of a stem thickening mixed 60% by weight, however, the dye compositions I

Parts of the resulting thickening, 6 parts by weight of and II of the following formulations instead of

Dye Composition A, 5 parts by weight of urea Dye Composition A were used.

Dye composition

(Parts by weight) I Il

C.I. Disperse Yellow 79 15 IS

Cresol / l-NaphthoI ^ -sulphonic acid 20 6

(Schäffersäure) / formaldehyde condensate (Dispersant)

Sodium dibutylnaphthalene sulfonate 2 2

Anhydrous sodium sulfate 5 4

Water 58 73

Dye compositions I and II were

by mixing and dispersing the above

Components prepared in an attritor for 2 hours (the same procedure was used as for the preparation of the dye preparations III to X as described above.)

A polyester jersey was made using each of Printing Pastes A, I and II by means of a flat screen printer printed with a 0.115mm screen. After drying, the printed matter became treated with high-temperature steam for 7 minutes at 180 ° C and then with a reducing Washed bath containing 2 g / l sodium hydrogen sulfite, 2 g / l sodium hydroxide and 3 g / l of a non-ionic surfactant, followed by washing with water and drying. One received articles which were printed in yellow. The color tones, relative surface densities and the color fastness characteristics the resulting colored products were determined and the results are in the table 3 listed.

laoene_ » Relative upper Rubbing fastness wet Fastness to perspiration alkaline hue Used surface color density dry angry Printing paste (A '/ S) 5 5 0.253 5 4th 5 4th strong bright yellow A. 0.229 5 4th 4th 4th slightly dull yellow I. 0.239 4th 4th slightly dull yellow II Example 3

Using the dye composition prepared in Example 1, a printing paste was made manufactured.

Esterified starch 9 parts by weight of sodium metanitrobenzenesulfonate 0.5 parts by weight of polyoxyethylene nonylphenol ether (product with 12 moles of ethylene oxide per mole of nonylphenol) 0.5 parts by weight of white spirit (bp. 170-180 ⁰ C 15 parts by weight of water 75% by weight) .-Parts

The above ingredients were uniformly incorporated in a high speed homogenizer Formation of a stem thickening mixed.

70 parts by weight of the resulting stem thickening. A parts by weight of the dye composition B, 5 parts by weight of urea and 21 parts by weight of water were introduced into a high-speed homogenizer and stirred for 15 minutes at a speed of 5000 rpm to form a printing paste B which had a viscosity of 650 ocP (determined using a B-type viscometer at 25 ° C).

For comparison purposes, printing pastes III and IV were prepared in the same way as above However, the dye compositions III and IV prepared in the usual way instead of dei Dye Composition B were used.

Dye IV 15th composition 4th (Parts by weight) C. I. Disperse Orange 73 III Cresol / I-naphthol-2-sulfonic acid 15th 2 (Shepherd's acid) / formaldehyde 10 condensate 2 Sodium naphthalenesulfonal / 4th Formaldehyde condensate 10 73 Sodium dibutyl naphlhalin sulfonate Sodium sulfate anhydrous 2 water 5 58

909 521/40:

Woven fabrics made from textured! Polyesters were produced using the resulting printing pastes B, III and IV printed in a rotary screen printing device with a 0.177 mm screen

After printing, the printed fabrics were treated with high pressure steam of 2 kg / cm ² for 30 minutes to fix the dye, washed with a reducing bath containing 2 g / l sodium hydrogen sulfite, 2 g / l sodium hydroxide and 3 g / l nonionic surfactant Contained agent, which was further washed with water and dried.

Orange-colored printed fabrics were obtained. The color tones, rlie relative surface color densities and the Color fastness characteristics were determined and the results are shown in Table 4.

Table 4 Relative upper Rubbing fastness wet Fastness to perspiration alkaline hue Used Making color density dry angry Printing paste (K / S) 4-5 5 0.319 4-5 3-4 5 4th strongly shining sound B. 0.292 3-4 3-4 4th 4th matt orange III 0.290 3-4 4th matt orange IV Example 4

Using the dye composition C prepared in Example 1, a printing paste was made prepares.

Ethereal strength

Sodium metanitrobenzenesulfonate

water

12 parts by weight
0.5 part by weight
87.5 parts by weight

These ingredients were uniformly mixed with a high speed homogenizer and 15 minutes at a speed of 5000 rpm to form a printing paste C having a viscosity of 900OcP (determined with a B type viscometer at 25 ⁰ C.).

For comparison purposes, pastes V and VI were prepared in the same way, but with the dye compositions V and VI of the following formulations, prepared in a conventional manner, instead of Dye Composition C were used.

dye Vl 15th composition 4th (Parts by weight) V 15th 10

CI. Disperse Blue 113
Cresol / i-naphthol-2-sulfonic acid (Schäfer's acid) / formaldehyde condensate

Sodium naphthalene sulfonate / 10 2

Formaldehyde condensate

Sodium dibutylnaphthalene sulfonate 2 2

Anhydrous sodium sulfate 5 4

Water 58 73

Polyesterfil / c were made with printing pastes C, V and VI printed by means of a flat screen printing device with a 0.115 mm screen.

After drying, the printed materials were ^{treated with high-temperature steam of 180 °} C. for 7 minutes, washed with a reducing bath containing 2 g / l sodium hydrogen sulfite, 2 g / l sodium hydroxide and 3 g / l of a non-ionic

Table V

surfactant, followed by water washed and dried.

Felts printed in blue were obtained. The color tones, the relative surface color densities and the color fastness characteristics the items were determined and the results are shown in Table 5.

Used Relative upper Rubbing fastness wet Fastness to perspiration alkaline hue Printing paste surface color density dry angry (K / S) 4-5 5 C. 0.339 5 3-4 5 4th strong bright blue V 0.272 4th 3-4 4th 4th matt blue Vl 0.286 4th 4th paints blue

Example 5

Dye baths of the following formulation were made using dye compositions B, C and D. of Example 1, and polyester knitted fabrics were prepared at high temperatures below the colored conditions given below.

Table 6

Used Dye Composition

Relative surface color density

(K / S)

hue

Dye bath formulation Ammonium sulfate 1 g / l acetic acid

(50% aqueous solution) 1 cm ³ / l

Leveling agent

(Polyoxyethylene lauryl sulfate adduct,

Ethylene oxide 7 mol) 2% o. W. F. Dye composition B, C or D 2 ^% o.w.f.

Solid

to liquid ratio 1:30

Dyeing temperature and time

The bath temperature was increased at a rate of 2.5 ^O C / min. raised to 130 ^° C., and the dyeing took place for 60 minutes at 130 ^° C.

After dyeing, the textiles were washed with a reducing bath because? 2 g / l sodium hydrogen sulfite, 2 g / l sodium hydroxide and 2 g / l one not ionic surfactant, followed by washing with water and drying. to For comparison purposes, polyester knitted fabrics were dyed in the same way as above, with however, the same dye compositions III and V as in Examples 3 and 4 were used and a dye composition VII of the following formulation was used in place of the dye compositions B, C and D.

ίο IV C.

VII

0.200

0.154
0.277

0.260
0.384

0.367

strong shining deep orange

slightly pale orange

strong shining deep blue

something pale blue

strong shining turquoise blue

matt turquoise blue

dye together setting VII (Parts by weight) C. I. Disperse Blue 198 15th Cresol / 1-naphthol-2-sulfonic acid (Sheep's acid) / formaldehyde condensate 10 Sodium naphthalene sulfonate / Formaldehyde condensate 10 Sodium dibutylnaphthalene sulfonate 2 Sodium sulfate anhydrous 5 water 58

Example 6

Using the dye composition E of Example ί, a pattern was made on a polyester taffeta imprinted by means of a roller printing machine with a gravure roller with a depth of 50 microns (100 lines / 244 cm).

After drying, the printed taffeta was heated to 180 ° C. with high temperature steam for 8 minutes heated to fix the dye, washed with a reducing bath containing 2 g / l sodium hydrogen sulfite, 2 g / l sodium hydroxide and 3 g / l one not

ίο ionic surfactant contained what on washed with water and dried.

For comparison purposes, printing was carried out in the same way as above, but using a dye composition VIII with the following formulation

J5 used in place of dye composition E. became.

Dye together
_4f) Settlement VIII

(Parts by weight)

C. I. Vat Red 4I = C. 1.73 300 10 Cresol / 1-naphthol-2-sulfonic acid

(Sheep's acid) / formaldehyde

condensate 10

Sodium dibutylnaphthalene

sulfonate 5

Sodium sulfate anhydrous 4 Carboxymethyl cellulose 3

Water 68

The relative surface color densities and the hues of the resulting colorations were determined, and the results are shown in Table 6.

The relative surface color densities, color fastness characteristics and color tones of the obtained articles were determined, and the results are listed in Table 7.

Table 7 Relative upper Rubbing fastness wet Sweaty laxity alkaline hue Used color surface color
concentraion dry angry S. composition (K / S) 4-5 5 ti
I. 0.343 4-5 3-4 5 4th strong bright red E. 0.310 4th 4th dull red; considerable VIII bleed out

Example 7

Using the dye composition F prepared in Example 1, a pattern was drawn up a nylon taffeta by means of a roller pressure device, equipped with a gravure roller with a depth of 45 microns (100 lines / 2.54 cm) printed.

After drying, the taffeta was steamed at 0.3 kg / cm ³ for 20 minutes to fix the

Dye treated, exposed to an alkaline soap (anhydrous soda 2 g / l and a non-ionic above surface-active agent 2 g / l), washed with water and dried.

For comparison purposes, printing was carried out in the same way as above, but with the dye composition IX of the following formulation was used in place of Dye Composition F.

Dye- together- settlement IX (Parts by weight) C. I. Acid Violet 103 10 Cresol / l-naphthol-2-sulfonic acid (SchäffersäureJ / formaldehyde- condensate 10 Sodium dibutylnaphthalene sulfonate 5 Sodium sulfate anhydrous 4th Carboxymethyl cellulose 3 water 68

The relative surface color densities, the color fastness characteristics and the hues of the resulting colored products were determined and the results are shown in Table 8.

Table 8

Dye composition

Relative upper-making color density

{K / S)

Rubbing fastness dry na Fastness to perspiration acidic alkaline

hue

E.
VIII

0.322
0.298

strong bright violet

dull purple; considerable bleeding

Example 8

Using the dye composition G prepared in Example 1, a printing paste was made manufactured.

12 parts by weight of etherified starch, 0.5 parts by weight of sodium metanitrosulfonate and 87.5 parts by weight of water were uniformly in a high speed homogenizer to form a stem thickening mixed.

70 parts by weight of the resulting thickening, 6 parts by weight of the dye composition G, 5 parts by weight Urea and 19 parts by weight of water were placed in a high speed homogenizer and 15 minutes at a speed of 5000 rpm to form a printing paste G with a Viscosity of 11,000 cP (determined in a viscometer of the B-type at 25 ° C) stirred.

For comparison purposes, a printing paste X was prepared in the same manner as above, wherein however, the fabric composition X of the following Formulation, prepared in the usual manner, was used in place of the dye composition G.

Dye composition X

(Parts by weight)

C. I. Basic Orange 33 15

Cresol / 1-naphthol-2-sulfonic acid

(SchäffersäureJ / Formaldahyd-

condensate 10

Sodium napi thalenesulfonate /

Formaldehyde condensate 5

Sodium dibutylnaphthalene

sulfonate 4

Sodium sulfate anhydrous 4

Water 62

Acrylic jersey was made using the resulting printing pastes G and X on a flat screen printing machine printed with a 0.115 mm screen.

After printing, the printed fabric was ^{treated by the steam setting method at 0.3 kg / cm 2 for} 10 minutes and subjected to an alkaline soap treatment.

gen (anhydrous soda 2 g / l and a non-ionic surfactant 3 g / l), washed with water and dried.
Articles printed in orange were obtained. The color tones, the relative surface color densities and the color fastness characteristics of the dyed products were determined, and the results are shown in Table 9.

Table 9 Relative upper
surface color density
(K / S) Rubbing fastness
(rock wet 5
4th Fastness to perspiration
acidic alkaline 5
5 hue Used
Printing paste 0.343
0.318 5
4-5 5
4th strong bright orange
matt orange Ci
X

B cis ρ ic I 9
Maleic Acid / Vinyl Acetate- (I / 10

3 parts by weight Ammonium salt * 5 parts by weight Polymeric H 30 parts by weight White spirit (bp 170-180 C) Polyoxy et hy lenoley lather 1 general part (12 mol of ethylene oxide added) 61 parts by weight water

The above ingredients were placed in a high speed mixer and carefully with the formation of a stem thickening of the emulsion type with a viscosity of 60,000 cP (determined in a B-type viscometer at 25 ° C) mixed.

2 parts by weight of the dye composition H of Example I, 60 parts by weight of the stock thickening, 5 Parts by weight of urea, 0.5 part by weight of sodium metanitrobenzenesulfonate and 32.5 parts by weight of water were used Stirred in a high speed mixer for 15 minutes to form a printing paste H.

Using the printing paste H, a nylon knitted fabric was made using a Flat screen printing machine printed with a screen of 0.115 mm.

After drying, the printed matter was ^{steam-fixed at 0.3 kg / cm 2 for} 20 minutes, subjected to an alkaline soap treatment (anhydrous soda 2 g / l, a nonionic surfactant 3 g / l), washed with water, and dried.

A bright yellow printed material was obtained which did not result in any staining. The printed fabric had a very good grip.

The ammonium salt of maleic acid / vinyl acetate copolymer was prepared as follows: a reactor equipped with a stirrer, a reflux condenser and a nitrogen gas inlet was charged with 12 parts by weight of maleic acid and 88 parts by weight of vinyl acetate charged, and 150 parts by weight of methanol and 0.02 parts by weight of azobisbutyronitrile were used as a solvent were added as a polymerization initiator. The reaction mixture was refluxed at 70 to Polymerized at 75 ° C until there was no more increase in the viscosity of the mixture (usually in 6 hours). After the polymerization, the methanol was evaporated under reduced pressure and sufficient Amount of 28% aqueous ammonia was added to the remaining polymer to neutralize it fed. The number average molecular weight of the resulting product was 4,000.

Example 10

Dye composition H 5 parts by weight

C. 1. Vat Yellow 2 = C. 1.67 300 5 parts by weight
Trunk thickening,

prepared as in Example 9, 50 parts by weight

Urea 5 parts by weight

Sodium m-nitrobenzenesulfonate 0.5 part by weight

Water 34.5 parts by weight

The above ingredients were placed in a high speed mixer and 15 minutes stirred to form a printing paste.

Polyester / cotton (50/50) jersey was made with the The resulting printing paste was printed using a rotary screen printing machine with a 0.177 mm screen.

After drying, the printed jersey was treated for 45 seconds at 200 ° C. with a solution of 60 g / l sodium hydrogen sulfite, 100 g / l sodium hydroxide (45 ° Be) and a 2% starch paste using a Treated applicator roller and passed for 30 seconds at 102 ° C through a »flash ager«, whereupon oxidation and Soap treatment was done in the usual way.

A bright yellow printed material with good color fastness was obtained

Claims (3)

Patent claims: Liquid type dye composition consisting of (1) a carrier composed of a water-soluble polymer having -COONH ₄ groups and a water-miscible organic solvent and optionally water, and (2) a water-insoluble or limited water soluble dye dispersed in the vehicle 2. Composition according to claim 1, characterized in that the water-soluble polymer 3 contains up to 20 -COONm groups per 100 g of the polymer 3. Composition according to claim 1, characterized in that the water-soluble polymer at least 3 mol%, preferably 5 to 35 mol%, of at least one repeating structural unit of the formula